EP0520109B1 - Polierbreie aus Silika mit geringem Gehalt an Natrium und an Metallen - Google Patents

Polierbreie aus Silika mit geringem Gehalt an Natrium und an Metallen Download PDF

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Publication number
EP0520109B1
EP0520109B1 EP91306014A EP91306014A EP0520109B1 EP 0520109 B1 EP0520109 B1 EP 0520109B1 EP 91306014 A EP91306014 A EP 91306014A EP 91306014 A EP91306014 A EP 91306014A EP 0520109 B1 EP0520109 B1 EP 0520109B1
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EP
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Prior art keywords
colloidal silica
present
ppm
silica slurry
sio2
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English (en)
French (fr)
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EP0520109A1 (de
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John A. Romberger
Charles C. Payne
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Rodel Inc
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Rodel Inc
Nalco Chemical Co
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/146—After-treatment of sols
    • C01B33/148—Concentration; Drying; Dehydration; Stabilisation; Purification
    • C01B33/1485—Stabilisation, e.g. prevention of gelling; Purification
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/141—Preparation of hydrosols or aqueous dispersions
    • C01B33/142—Preparation of hydrosols or aqueous dispersions by acidic treatment of silicates
    • C01B33/143—Preparation of hydrosols or aqueous dispersions by acidic treatment of silicates of aqueous solutions of silicates
    • C01B33/1435—Preparation of hydrosols or aqueous dispersions by acidic treatment of silicates of aqueous solutions of silicates using ion exchangers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1454—Abrasive powders, suspensions and pastes for polishing
    • C09K3/1463—Aqueous liquid suspensions

Definitions

  • the present invention provides novel colloidal silica slurries having a low sodium and metal content which are particularly useful in the polishing of silicon wafers or substrates.
  • Silicon wafers are basic components of integrated circuits, semiconductors devices, and transistors. adhesive.
  • dilute colloidal silica is continuously injected between the polishing plate and the silicon wafer for fine polishing of the wafer.
  • the electrical performance of finished semiconductor chips can easily be affected by contaminants acquired by the wafers during processing.
  • contamination can be in the form of discrete particles and water soluble or dispersed organic and inorganic impurities. That is, the use of silica sols that are contaminated with trace transition metals, alkali and alkaline earth metals, aluminum, and the like have caused difficulties especially when used in wafer polishing.
  • contaminating metals are particularly a nuisance when they include Na, K, alkali and alkaline earth metals such as Ca, Mg, and transition metals such as Fe, Cu, Mn, Ni, Zn, and the like.
  • any transition metal from groups IB, IIB, IIIB, IVB, VB, VIB, and group VIII of the Periodic Table of Elements if present in high enough concentrations, can cause difficulties in the final products manufactured with silica sols containing these contaminants.
  • Alkali metals like lithium, sodium, and potassium demonstrate shifts in electrical properties (threshold and flat-band voltages) when incorporated into semiconductor devices.
  • Heavy metals, such as copper, gold and iron, tend to lower minority carrier lifetime, while increasing dark and leakage currents. Tin, nickel and chromium behave similarly except that they also exhibit a lower oxide breakdown voltage.
  • colloidal silica containing metals will contaminate the wafer surface. Therefore, it is extremely desirable that colloidal silica products be formed with low sodium and metals content.
  • the Sasaki et al. patent discloses a method for producing an aqueous low alkali-metal, low alumina silica sol by treatment of a powder silica with acid to remove the metals while applying ultrasonic vibrations.
  • Spencer discloses a process for preparing finely divided metallic oxides by hydrolyzing a compound containing the corresponding metal while in contact with a finely divided carbonaceous carrier on which the oxide is deposited and then separating the oxide from the carbon.
  • the Stober article discloses a system of chemical reactions which permit the controlled growth of spherical silica particles of uniform size by means of hydrolysis of alkyl silicates and subsequent condensation of silicic acid in alcoholic solutions.
  • Ammonia is used as a morphological catalyst.
  • Low sodium silica sol products with or without low metal content, can also be prepared by removal of the counterions using ion exchange and then backadding ammonium hydroxide and ammonium carbonate to form stable products according to the Iler article.
  • colloidal silica is normally used in a once through polishing system, the cost of the silica and chemicals admixed therewith have caused an increased interest in the development of commercially acceptable recirculation systems.
  • Recirculation systems provide fast polishing rates without high temperatures, avoid wafer warping, and substantially reduce the chemical cost of the polishing step.
  • colloidal silicas, with or without organic accelerators are placed in service for prolonged periods of time they exhibit increased microorganism and fungi growth. Bacterial contamination causes discoloration, odors, and makes the colloidal silica unacceptable as a polishing aid in wafer production.
  • the Michalski '236 patent discloses a method for protecting aqueous colloidal silica sols from bacterial contamination.
  • This patent suggests that colloidal aqueous silica sols can be protected from bacterial contamination by simply adding sodium chlorite in an amount sufficient to inhibit growth and reproduction of the bacteria.
  • sodium chlorite Generally from about 10 parts of sodium chlorite per million parts of slurry up to about 1000 parts per million achieve the desired situation of freedom from bacterial contamination.
  • the Havens patent suggests that colloidal silica aquasols containing about 10-1000 parts per million of hexachlorophene can be protected from contamination by microorganisms. Addition of the hexachlorophene is intended to prevent discoloration, bad odor, and slime formation and increase the shelf life of colloidal silica sols to more than one year.
  • the Payne '431 and Nickerson patents are concerned with controlling bacterial growth in silica aquasols containing polyhydric alcohols.
  • Payne 431' attempts to control and eliminate the growth of organisms such as aerobacter and pseudomonus bacteria, aspergillus niger mold, and troublesome desulfovibio and clostridia anaerobic bacteria by addition of a biocide.
  • Typical biocides are glutaraldehyde, ethylenediamine, hydrogen peroxide and methyl p-hydroxybenzoate.
  • Nickerson suggests that the addition of sodium pentachlorophenate will prevent or inhibit the darkening of silica aquasol containing polyhydric alcohol even in those instances where the silica aquasol contains sodium sulfate.
  • the Yoder and Roman et al. patents disclose the use of dialdehydes, such as glutaraldehyde, to control bacteria. While Michalski et al. '275 and McGahen disclose the use of formaldehyde to protect colloidal silica sols from bacteria growth. McGahen also discloses the use of 3,5-dimethyl tetrahydro 1,3,5,2-H-thiadiazine-2-thione as a microbiocide.
  • Payne '337, Payne '188, Payne '421, and Huff '612 disclose the use of various polishing rate accelerator amines added to conventional colloidal silica to form acceptable polishing agents and in particular Payne '188 discloses a water-based composition comprising silica sol, an amine such as triethylene tetramine and a quaternary ammonium salt such as tetramethylammoniumhydroxide, to be used as a polishing agent for polishing silicon wafers, while Payne '421 discloses a similar composition comprising as the amide piperazine. This agent moreover acts as a microbiocidal agent.
  • these patents are not concerned with either a low metals, low sodium colloidal silica or with a polishing agent which can be recirculated without increased microorganism or fungi growth.
  • Kohyama et al. discloses an aqueous dispersion of silicic anhydride having a silica particle size in the range between about 100 nm to 10,000 nm which is prepared from a dry method.
  • PH controlling agents such as amines, may be added to the silicic anhydride of Kohyama et al.
  • the silicas prepared according to Kohyama et al. exhibit the following characteristics: (1) the particles are prepared by a dry method which can then be dispersed into a fluid medium, (2) the particles are not discrete but exist as condensed masses or aggregates, and (3) the aggregates settle with time and hence do not fit the historical definition of a silica colloid.
  • Kohyama et al. concerned with low metals, low sodium colloidal silica or control of microorganism or fungi growth in recirculating systems.
  • EP-A-0146313 discloses a highly pure aqueous silica sol which is stabilized in the acidic pH range.
  • the present inventors have found that although no microbiological growths are present in conventional colloidal silica at the outset, increased microbiological growth is observed during recirculation and dilution of the slurry. These microbiological growths are promoted when organic rate accelerators are used.
  • the present inventors undertook the task of examining the recirculation polishing system and developing a novel group of colloidal silica slurries which eliminate bacterial and fungi growth, maintain and, in some instances, increase the polishing rate of the system, and provide a polishing medium with extremely low values, particularly of Al, Fe, K, Na, and the other transition metals as described above.
  • colloidal silica slurries which are capable of inhibiting bacterial growth and enhancing the polishing rate of silicon wafers.
  • colloidal silica slurries are formed from a low metal, ammonium-stabilized silica sol that has particle sizes ranging from about 4 to about 130 nanometers. This sol has discrete spherical particles, and finds particular use in high quality investment casting, high technology refractories, catalyst applications, electronic polishing agents, and in high technology coating applications.
  • the novel colloidal silica slurry of the present invention comprises: a low metals ammonium-stabilized silica sol having the following characteristics: SiO2 present in the range between 15 to 50 weight percent; a pH in the range between 8.5 to 11.3; a particle diameter in the range between 3.0 to 130 nm; aluminum, as Al, present in an amount less than about 100 ppm based on SiO2; iron, as Fe, present in an amount less than about 50 ppm based on SiO2; potassium, as K, present in an amount less than about 25 ppm based on SiO2; and sodium, as Na, present in an amount less than about 500 ppm based on SiO2; 0.08 to 5% of an ammonium-containing bactericide; alternatively a polishing rate accelerator in an amount of 0.5 to 5% and in either case optionally up to 1000 ppm of a sodium chlorite or sodium hypochlorite biocide.
  • a fungicide may be added to the slurry to inhibit fung
  • An additional object of the present invention is a process for polishing a silicon wafer which includes the step of recirculating the novel colloidal silica slurry of the present invention between a polishing plate containing a polishing pad and the silicon wafer, the improvement characterized by the use of a colloidal silica slurry defined as above.
  • the present invention may also include many additional features which shall be further described below.
  • Silicon wafers or substrates are basic components of integrated circuits, semiconductor devices, and transistors.
  • Low sodium, low metal impurity silica products for recirculated wafer polishing systems can be prepared from low metal silica sources, such as tetramethyl- or tetraethyl-orthosilicate or silicon tetrachloride.
  • the colloidal silicas can be prepared from these materials by a controlled hydrolysis reaction, although any procedure which yields low metals can be used.
  • the products can be stabilized with the addition of counterions.
  • the counterions may be selected from ammonium hydroxide, amines, quaternary ammonium hydroxides (tetramethyl-or tetraethyl-ammonium hydroxide), or mixtures thereof. Although it has been found to be highly desirable to stabilize the resultant sol with ammonium hydroxide.
  • a low metal, ammonium-stabilized silica sol can be made using the following steps:
  • the colloidal silica slurry according to the present invention comprises: a low metals ammonium-stabilized silica sol having the following characteristics: SiO2 present in the range between 15 to 50 weight percent; a pH in the range between 8.5 to 11.3; a particle diameter in the range between 3.0 to 130 nm; aluminum, as Al, present in an amount less than 100 ppm based on SiO2; iron, as Fe, present in an amount less than 50 ppm based on SiO2; potassium, as K, present in an amount less than about 25 ppm based on SiO2; and sodium, as Na, present in an amount less than 500 ppm based on SiO2; a bactericide present in an amount between 0.08 to 5%, the bactericide being at least one compound selected from the group consisting of tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetramethylammonium hydroxide, te
  • the polishing rate accelerator if present, is generally of an amount up to 5%.
  • the bactericide is present in an amount between 0.08-5%, preferably 0.5-0.75%.
  • the biocide is present in an amount up to 1000 ppm, preferably 500 ppm, and more preferably 65-100 ppm.
  • the fungicide is added to the colloidal silica slurry in an amount up to 2.0%, 0.8%, and more preferably in the range 0.1-0.5%.
  • the colloidal silica slurry may comprise: a low metals ammonium-stabilized silica sol having the following characteristics: SiO2 present in the range between 15 to 50 weight percent; a pH in the range between 8.5 to 11.3; a particle diameter in the range between 3.0 to 130 nm; aluminum, as Al, present in an amount less than 100 ppm, based on SiO2; iron, as Fe, present in an amount less than 50 ppm based on SiO2; potassium, as K, present in an amount less than about 25 ppm based on SiO2; and sodium, as Na, present in an amount less than about 500 ppm based on SiO2; and a polishing rate accelerator present in an amount between 0.5 to 5%.
  • a sodium chlorite or sodium hypochlorite biocide and/or a fungicide may also be added as required.
  • the colloidal silica is preferably prepared in accordance with the aforementioned method disclosed in co-pending EP-A-0464289.
  • the discrete spherical particles formed in that process are different from the chain-like particles that are formed in other processes attempting to achieve very low-metals silica sols.
  • a silica sol is formed having characteristics, after concentration, preferably by ultra-filtration, as follows: Silica, as SiO2, of 15-50 weight percent, pH, as adjusted with ammonia, ranging from between about 8.5-11.3, and Particle Diameter ranging from about 4.0 to 130 nm.
  • this silica sol has less than 100 ppm, Al, less than 50 ppm Fe, less than 25 ppm, less than 500 ppm Na, all based on SiO2.
  • This process can be also be optimized to form silica sols which are low-metals, ammonium-stabilized silica sols having the following characteristics.
  • another silica sol has the following characteristics: SiO2 30 ⁇ 2.5 weight percent pH 9.0 ⁇ 0.25 Particle Diameter 5 to 30 nm Aluminum, as Al ⁇ 30 ppm, based on SiO2 Iron, as Fe ⁇ 15 ppm, based on SiO2 Potassium, as K ⁇ 10 ppm, based on SiO2 Sodium, as Na ⁇ 100 ppm, based on SiO2
  • Still another silica sol has the following characteristics: SiO2 30 ⁇ 2.5 weight percent pH 9.0 ⁇ 0.25 Particle Diameter 30 to 100 nm Aluminum, as Al ⁇ 30 ppm, based on SiO2 Iron, as Fe ⁇ 15 ppm, based on SiO2 Potassium, as K ⁇ 10 ppm, based on SiO2 Sodium, as Na ⁇ 100 ppm, based on SiO2
  • the polishing rate accelerator can be any amine/nitrogen compound. However, it is preferable that the polishing rate accelerator be at least one compound selected from the group consisting of: primary amines, secondary amines, tertiary amines, heterocyclic amines, and mixtures thereof. Quaternary amines can be used, but only in combination with one of the other types of amines. It is intended that the above classification include all blends thereof which are known to those skilled in the art. Provided, however, that the polishing rate accelerator cannot be a quaternary amine when used in conjunction with quaternary amine bactericides.
  • Examples of primary amines are monoethanolamine, isopropylamine, ethylenediamine, and propanediamine.
  • Examples of secondary amines are diethanolamine, dipropylamine, and dibutylamine.
  • An example of a tertiary amine is triethanolamine.
  • Examples of quaternary amines are tetramethylammonium chloride or hydroxide, tetraethylammonium chloride or hydroxide, tetrapropylammonium chloride or hydroxide, alkylbenzyldimethylammonium chloride or hydroxide, wherein the alkyl chain ranges from 1 to about 20 carbons.
  • heterocyclic amines examples include hexamethylenediamine, bis(aminopropyl) piperazine, and piperazine.
  • the polishing rate accelerator may also be one compound selected from the group consisting of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and aminoethylethanolamine.
  • the bactericide is at least one compound selected from the group consisting of: tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, alkylbenzyldimethylammonium hydroxide, and alkylbenzyldimethylammonium chloride, wherein the alkyl chain ranges from 1 to about 20 carbons.
  • Preferred bactericides are those capable of serving a dual function, i.e., being a bactericide and a polishing rate enhancer.
  • the preferred biocide is sodium chlorite or sodium hypochlorite.
  • the preferred fungicide is sodium OMADINE® (pyrithione).
  • the novel colloidal silica slurry of the present invention is preferably used in a process for polishing a silicon wafer.
  • the silicon wafer polishing process includes the step of recirculating one of the colloidal silica slurries as previously defined, between a polishing plate containing a polishing pad and the silicon wafer.
  • TMA-OH bactericide tetramethylammonium hydroxide
  • Tetramethylammonium chloride may also be used with the same effect.
  • Sample 1 is deionised water
  • sample 2 is a conventional colloidal silica used in the polishing of silicon wafers
  • sample 3 is a low sodium, low metals colloidal silica slurry in accordance with the present invention.
  • the microbiological test procedures used in generating the following results were as follows: (1) Dilute one part product with 20 parts water (do not make a pH adjustment); (2) Challenge the product with a bacteria/mold inoculum consisting of: (a) Aspergillus niger, (b) Pseudomonus aeruginosa, and (c) Aerobacter aerogenes; (3) Place the inoculated sample on a rotating shaker in a room conditioned at 37°C (rotate at 100 rpm continuously); and (4) Sample at zero time, one week, and two weeks.
  • the organisms are grown under the following conditions: (a) Total count - run at 37°C for 72 hours using TGE agar (tryptone-glucose extract), (b) Aspergillus -run at 30°C for 96 hours using potato dextrose, and (c) Aerobacter - run at 37°C for 24 hours using EMB agar (eosin methylene blue).
  • Table 1 below shows the results of the microbiological testing. A 99.0% or greater kill is considered an acceptable colloidal silica slurry.
  • Table 1 demonstrates the effect of the TMA-OH with and without sodium Omadine® on bacteria and mold. The results indicate that 0.68% active TMA-OH with sodium chlorite and sodium OMADINE® (pyrithione) will inhibit the products after one or two weeks.
  • a colloidal silica slurry according to the present invention was prepared and evaluated verses conventional colloidal silicas.
  • Sample 1 is a conventional colloidal silica containing 2% aminoethylethanolamine (AEEA)
  • sample 2 is a conventional colloidal silica containing 5% piperazine
  • sample 3 is a low sodium, low metals colloidal silica slurry according to the present invention.
  • the polishing machine was a Fujikosi four head 68.6 cm (27") machine having a platen of 68.6 cm (27") diameter with four polishing heads, capable of holding three 10.5 cm (4") wafers.
  • the wafers were P-100 type; boron doped; 10.5 cm (4") diameter; acid etched.
  • Silica level was 3.53% as SiO2.
  • the polishing pad was a 68.6 cm (27") diameter Suba 600.
  • polishing conditions for the field trials were as follows: polishing pressure of 370 g/cm2 (5.2 lb/in2), polishing speed of 50 RPM (platen), polishing temperature of 26°-30°, a pH of 10.7-9.7 (start to finish), KOH caustic, a flow rate of 2000 mL/min. (recirculated), and a total removal amount of 15 micrometers.
  • the field test results were obtained using the following polishing test procedures: (1) Place new polishing pad on machine; (2) Dress the pad by first rinsing with deionized water and then scraping the pad with a razor blade; (3) Load a set of wafers on the machine; (4) Start the slurry flow to purge the lines and soak the pad; (5) Make a service run at the desired pressure and flow rate; (6) After the service run is over, rinse the wafers, remove from the carriers and replace with more wafers; (7) Place in hot ( ⁇ 170°F) water for a period of 5-10 minutes; and (8) Air dry the wafers.
  • Table 3 compares the polishing rates of the colloidal silica slurry of the present invention (Sample 3) verses conventional colloidal silicas (Samples 1 and 2) using the same polishing conditions.
  • the present invention was stabilized with ammonia instead of sodium as in samples 1 and 2, and resulted in a polishing rate equivalent to or greater than the conventional colloidal silicas while maintaining reduced sodium levels.
  • Silicon wafers can be polished using high purity colloidal silicas prepared in accordance with the procedures set forth in EP-A-0464289. A 30% ammonium-stabilized silica sol having a particle diameter of about 14.4 nm was prepared in accordance with those procedures (Sample 1). Table 5 below lists the metal analyses as done by Ion Coupled Argon Plasma (ICP) of Sample 1. The total metal content based on the average of analyses 1 and analyses 2 is 256 ppm.
  • ICP Ion Coupled Argon Plasma
  • Sample 1 was tested on a Siltec 3800 polishing machine against Sample 2 (i.e., a 50% conventional colloidal silica sol having a particle diameter in the range between about 50-70 nm), and Sample 3 (i.e., Sample 1 with an AEEA polishing rate accelerator).
  • the operating conditions for the silicon wafer polishing was as follows: Number of Polishing Heads 4 x 53 cm (21-inch) diameter Polishing Speed 65 rpm Polishing Pressure 3,900 kg/m2(5.55 lb/in2) Polishing Time 20 minutes Flow Rate 189 ml /minute Temperature 42 to 45°C SiO2 Concentration 2.8% Polishing pH 11.0 Caustic Used 45% KOH

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Claims (23)

  1. Verfahren zur Herstellung einer kolloidalen Silika-Aufschlämmung, umfassend das Vermischen:
       eines ammonium-stabilisierten Silikasols mit niedrigem Metallgehalt mit den folgenden Merkmalen: SiO₂, enthalten im Bereich von 15 - 50 Gew.-%; einen pH im Bereich von 8,5 - 11,3; einen Teilchendurchmesser im Bereich von 3,0 - 130 nm; Aluminium, als Al, enthalten in einer Menge von weniger als 100 ppm, bezogen auf SiO₂; Eisen, als Fe, enthalten in einer Menge von weniger als 50 ppm, bezogen auf SiO₂; Kalium, als K, enthalten in einer Menge von weniger als 25 ppm, bezogen auf SiO₂; und Natrium, als Na, enthalten in einer Menge von weniger als 500 ppm, bezogen auf SiO₂;
       eines in einer Menge von 0,08 - 5% enthaltenen Bakterizids, das zumindest eine Verbindung, ausgewählt aus der aus Tetramethylammoniumchlorid, Tetraethylammoniumchlorid, Tetrapropylammoniumchlorid, Tetramethylammoniumhydroxid, Tetraethylammoniumhydroxid, Tetrapropylammoniumhydroxid, Alkylbenzyldimethylammoniumchlorid und Alkylbenzyldimethylammoniumhydroxid bestehenden Gruppe, ist, worin die Alkylkette im Bereich von 1 - 20 Kohlenstoffatomen liegt; und
       von Natriumchlorit oder Natriumhypochlorit in einer Menge von 0 - 1000 ppm.
  2. Verfahren nach Anspruch 1, worin das Bakterizid in einer Menge von 0,1 - 1,25% zugemischt wird.
  3. Verfahren nach Anspruch 2, worin das Bakterizid in einer Menge von 0,5 - 0,75% zugemischt wird.
  4. Verfahren nach irgendeinem der vorangegangenen Ansprüche, worin das Natriumchlorit oder Natriumhypochlorit in einer Menge von 65 - 100 ppm zugemischt wird.
  5. Verfahren nach irgendeinem der vorangegangenen Ansprüche, das weiters das Zumischen eines Fungizids in einer Menge von bis zu etwa 2,0% umfaßt.
  6. Verfahren nach Anspruch 5, worin das Fungizid in einer Menge von 0,1 - 0,5% zugemischt wird.
  7. Verfahren nach Anspruch 5 oder 6, worin das Fungizid Natriumpyrithion ist.
  8. Verfahren nach irgendeinem der vorangegangenen Ansprüche, das weiters das Zumischen eines Polierraten-Beschleunigers in einer Menge von 0,5 - 5% umfaßt, wobei der Polierraten-Beschleuniger zumindest einer aus: primären Aminen, sekundären Aminen, heterozyklischen Aminen, Diethylentriamin, Triethylentetramin, Tetraethylenpentamin und Aminoethylethanolamin und Gemischen davon ist.
  9. Verfahren zur Herstellung einer kolloidalen Silika-Aufschlämmung, umfassend das Vermischen:
       eines ammonium-stabilisierten Silikasols mit niedrigem Metallgehalt mit den folgenden Merkmalen: SiO₂, enthalten im Bereich von 15 - 50 Gew.-%; einen pH im Bereich von 8,5 - 11,3; einen Teilchendurchmesser im Bereich von 3,0 - 130 nm; Aluminium, als Al, enthalten in einer Menge von weniger als 100 ppm, bezogen auf SiO₂; Eisen, als Fe, enthalten in einer Menge von weniger als etwa 50 ppm, bezogen auf SiO₂; Kalium, als K, enthalten in einer Menge von weniger als 25 ppm, bezogen auf SiO₂; und Natrium, als Na, enthalten in einer Menge von weniger als 500 ppm, bezogen auf SiO₂; und
       eines Polierraten-Beschleunigers in einer Menge von 0,5 - 5%.
  10. Verfahren nach Anspruch 9, worin der Polierraten-Beschleuniger zumindest eine Verbindung aus: primären Aminen, sekundären Aminen, tertiären Aminen, heterozyklischen Aminen und Gemischen davon ist.
  11. Verfahren nach Anspruch 8 oder 10, worin das primäre Amin Monoethanolamin, Isopropylamin, Ethylendiamin oder Propandiamin ist.
  12. Verfahren nach Anspruch 8 oder 10, worin das sekundäre Amin Diethanolamin, Dipropylamin oder Dibutylamin ist.
  13. Verfahren nach Anspruch 8 oder 10, worin das heterozyklische Amin Hexamethylendiamin, Bis-(Aminopropyl)piperazin oder Piperazin ist.
  14. Verfahren nach Anspruch 10, worin der Polierraten-Beschleuniger zumindest ein quaternäres Amin umfaßt.
  15. Verfahren nach Anspruch 10, worin das tertiäre Amin Triethanolamin ist.
  16. Verfahren nach Anspruch 14, worin das quaternäre Amin aus der aus Tetramethylammoniumchlorid, Tetraethylammoniumchlorid, Tetrapropylammoniumchlorid, Tetramethylammoniumhydroxid, Tetraethylammoniumhydroxid, Tetrapropylammoniumhydroxid, Alkylbenzyldimethylammoniumchlorid und Alkylbenzyldimethylammoniumhydroxid bestehenden Gruppe ausgewählt wird, worin die Alkylkette im Bereich von 1 - 20 Kohlenstoffatomen liegt.
  17. Verfahren nach Anspruch 9 oder 10, worin der Polierraten-Beschleuniger aus der aus Diethylentriamin, Triethylentetramin, Tetraethylenpentamin und Aminoethylethanolamin bestehenden Gruppe ausgewählt wird.
  18. Verfahren nach Anspruch 9, 10 oder 17, das weiters das Zumischen von Natriumchlorit oder Natriumhypochlorit in einer Menge von 1 - 1000 ppm umfaßt.
  19. Verfahren nach Anspruch 9, 10, 17 oder 18, worin entweder das Natriumchlorit oder das Natriumhypochlorit in einer Menge von 65 - 100 ppm zugemischt wird.
  20. Verfahren nach Anspruch 9, 10, 17, 18 oder 19, das weiters das Zumischen eines Fungizids in einer Menge von bis zu etwa 2,0% umfaßt.
  21. Verfahren nach Anspruch 20, worin das Fungizid in einer Menge von 0,1 - 0,5% zugemischt wird.
  22. Verfahren nach Anspruch 20 oder 21, worin das Fungizid Natriumpyrithion ist.
  23. Verfahren zum Polieren eines Silizium-Wafers, das den Schritt des Rezirkulierens einer kolloidalen Silika-Aufschlämmung nach irgendeinem der vorangegangenen Ansprüche zwischen einer Polierplatte umfaßt, die ein Polierkissen und den Silizium-Wafer enthält.
EP91306014A 1991-05-28 1991-07-02 Polierbreie aus Silika mit geringem Gehalt an Natrium und an Metallen Expired - Lifetime EP0520109B1 (de)

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US70632191A 1991-05-28 1991-05-28
US706321 1991-05-28

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EP0520109B1 true EP0520109B1 (de) 1995-03-29

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EP (1) EP0520109B1 (de)
KR (1) KR0184010B1 (de)
AT (1) ATE120433T1 (de)
DE (1) DE69108546T2 (de)
FI (1) FI914594A (de)
MY (1) MY108609A (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10695744B2 (en) 2015-06-05 2020-06-30 W. R. Grace & Co.-Conn. Adsorbent biprocessing clarification agents and methods of making and using the same

Families Citing this family (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2738291B2 (ja) * 1994-02-14 1998-04-08 日本電気株式会社 機械・化学研磨方法および研磨装置
JP2894208B2 (ja) * 1994-06-02 1999-05-24 信越半導体株式会社 シリコンウェーハ研磨用研磨剤及び研磨方法
SG54606A1 (en) * 1996-12-05 1998-11-16 Fujimi Inc Polishing composition
KR19990023544A (ko) * 1997-08-19 1999-03-25 마쯔모또 에이찌 무기 입자의 수성 분산체와 그의 제조 방법
WO1999032570A1 (en) * 1997-12-23 1999-07-01 Akzo Nobel N.V. A composition for chemical mechanical polishing
KR20000019872A (ko) * 1998-09-16 2000-04-15 유현식 웨이퍼 절연층 연마용 슬러리의 제조방법
JP2000160139A (ja) * 1998-12-01 2000-06-13 Fujimi Inc 研磨用組成物およびそれを用いた研磨方法
FR2789998B1 (fr) * 1999-02-18 2005-10-07 Clariant France Sa Nouvelle composition de polissage mecano-chimique d'une couche en un materiau conducteur d'aluminium ou d'alliage d'aluminium
KR20010004982A (ko) * 1999-06-30 2001-01-15 김영환 반도체 소자의 산화막 연마용 슬러리 제조 방법
CN1199856C (zh) * 1999-12-20 2005-05-04 阿克佐诺贝尔公司 含水氧化硅基溶胶及其制备方法和用途
KR100396881B1 (ko) * 2000-10-16 2003-09-02 삼성전자주식회사 웨이퍼 연마에 이용되는 슬러리 및 이를 이용한 화학기계적 연마 방법
TWI228538B (en) * 2000-10-23 2005-03-01 Kao Corp Polishing composition
DE10063488A1 (de) * 2000-12-20 2002-06-27 Bayer Ag Polierslurry für das chemisch-mechanische Polieren von Siliciumdioxid-Filmen
KR100445499B1 (ko) * 2001-07-23 2004-08-21 제일모직주식회사 반도체 디바이스의 산화막 연마용 ｃｍｐ 슬러리
KR100474539B1 (ko) * 2002-07-15 2005-03-10 주식회사 하이닉스반도체 반도체 소자의 제조 방법
DE10247202A1 (de) * 2002-10-10 2003-10-30 Wacker Siltronic Halbleitermat Verfahren zur Herstellung einer polierten Siliciumscheibe mit niedrigem Kupfergehalt
US7192886B2 (en) * 2002-10-25 2007-03-20 Intersurface Dynamics, Inc. Method for using additives in the caustic etching of silicon for obtaining improved surface characteristics
US7005382B2 (en) * 2002-10-31 2006-02-28 Jsr Corporation Aqueous dispersion for chemical mechanical polishing, chemical mechanical polishing process, production process of semiconductor device and material for preparing an aqueous dispersion for chemical mechanical polishing
GB0328530D0 (en) * 2003-12-09 2004-01-14 Syngenta Ltd Agrochemical composition
JP2005268667A (ja) * 2004-03-19 2005-09-29 Fujimi Inc 研磨用組成物
US8017524B2 (en) * 2008-05-23 2011-09-13 Cabot Microelectronics Corporation Stable, high rate silicon slurry
US8697576B2 (en) 2009-09-16 2014-04-15 Cabot Microelectronics Corporation Composition and method for polishing polysilicon
US8815110B2 (en) * 2009-09-16 2014-08-26 Cabot Microelectronics Corporation Composition and method for polishing bulk silicon
US8883034B2 (en) 2009-09-16 2014-11-11 Brian Reiss Composition and method for polishing bulk silicon
US11628381B2 (en) 2012-09-17 2023-04-18 W.R. Grace & Co. Conn. Chromatography media and devices
MY195756A (en) 2012-09-17 2023-02-09 Grace W R & Co Functionalized Particulate Support Material and Methods of Making and Using the Same
JP6853670B2 (ja) 2014-01-16 2021-04-07 ダブリュー・アール・グレース・アンド・カンパニー−コーンＷ Ｒ Ｇｒａｃｅ ＆ Ｃｏ−Ｃｏｎｎ 親和性クロマトグラフィー媒体及びクロマトグラフィーデバイス
ES2929099T3 (es) 2014-05-02 2022-11-24 Grace W R & Co Material de soporte funcionalizado y métodos de fabricación y uso de material de soporte funcionalizado
WO2016115096A1 (en) * 2015-01-12 2016-07-21 Air Products And Chemicals, Inc. Composite abrasive particles for chemical mechanical planarization composition and method of use thereof

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3816330A (en) * 1970-10-05 1974-06-11 Du Pont Method of protecting colloidal silica aquasols from bacterial degradation
US4462188A (en) * 1982-06-21 1984-07-31 Nalco Chemical Company Silica sol compositions for polishing silicon wafers
JPS60127216A (ja) * 1983-12-10 1985-07-06 Nitto Chem Ind Co Ltd 低アルカリ低アルミナ含量の水性シリカゾルの製造法
US4588421A (en) * 1984-10-15 1986-05-13 Nalco Chemical Company Aqueous silica compositions for polishing silicon wafers
JP2714411B2 (ja) * 1988-12-12 1998-02-16 イー・アイ・デュポン・ドゥ・ヌムール・アンド・カンパニー ウェハーのファイン研摩用組成物

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10695744B2 (en) 2015-06-05 2020-06-30 W. R. Grace & Co.-Conn. Adsorbent biprocessing clarification agents and methods of making and using the same

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FI914594A0 (fi) 1991-09-30
ATE120433T1 (de) 1995-04-15
EP0520109A1 (de) 1992-12-30
FI914594A (fi) 1992-11-29
KR920021685A (ko) 1992-12-18
DE69108546T2 (de) 1995-11-30
KR0184010B1 (ko) 1999-04-01
MY108609A (en) 1996-10-31
DE69108546D1 (de) 1995-05-04

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